CN114620818A - Flocculating agent and preparation method thereof - Google Patents
Flocculating agent and preparation method thereof Download PDFInfo
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- CN114620818A CN114620818A CN202210297366.4A CN202210297366A CN114620818A CN 114620818 A CN114620818 A CN 114620818A CN 202210297366 A CN202210297366 A CN 202210297366A CN 114620818 A CN114620818 A CN 114620818A
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- 239000008394 flocculating agent Substances 0.000 title claims description 11
- 239000000178 monomer Substances 0.000 claims abstract description 103
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- 239000003999 initiator Substances 0.000 claims abstract description 43
- 125000002091 cationic group Chemical group 0.000 claims abstract description 41
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- 238000000034 method Methods 0.000 claims description 20
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- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims description 15
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
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- PZDUWXKXFAIFOR-UHFFFAOYSA-N hexadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C=C PZDUWXKXFAIFOR-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
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- XSHISXQEKIKSGC-UHFFFAOYSA-N 2-aminoethyl 2-methylprop-2-enoate;hydron;chloride Chemical compound Cl.CC(=C)C(=O)OCCN XSHISXQEKIKSGC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 241001073224 Baeopogon indicator Species 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
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- 150000001336 alkenes Chemical class 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention belongs to the field of flocculant materials, and discloses a flocculant which is used as a prepared emulsion and comprises a copolymer formed by polymerizing a plurality of monomers, wherein the copolymer comprises: polyacrylamide monomer as main monomer group, poly N, N-dimethyl-octadecyl allyl ammonium chloride monomer as ion monomer group, and poly hexadecyl acrylate monomer as hydrophobic monomer group; wherein the ionic monomer is embedded on the polyacrylamide carbon chain to form a block type copolymer, the cationic degree in the copolymer is 20-50%, and the viscosity average molecular weight is 300-500 ten thousand. The preparation process includes compounding monomer into liquid A and initiator into liquid B, and titration reaction under certain condition. The cationic hydrophobic association type polyacrylamide synthesized by the suspension polymerization method has low viscosity, easily-derived polymerization heat, lower production cost and less three wastes compared with bulk polymerization and solution polymerization, and the heat dissipation and temperature control are easy.
Description
Technical Field
The invention belongs to the technical field of flocculating agents, and particularly relates to a flocculating agent and a preparation method thereof.
Background
At present, methods for sewage treatment are mainly divided into three major categories, namely physical methods, chemical methods and biological methods. The physical method mainly comprises filtration, physical adsorption, extraction and centrifugation, and the method has some limitations and can not change the chemical properties of pollutants, so the effect is not very obvious; chemical methods are a way to make pollutants harmless by changing their chemical structure, composition, etc. using chemical reactions or physicochemical changes. The biological method mainly comprises the technical means of chemical adsorption, oxidation-reduction, chemical precipitation, flocculation-sedimentation, ion exchange and the like, and utilizes the strong physiological metabolism of cells in vivo to metabolize and convert part of organic matters into energy required by the cells or decompose stable, nontoxic and harmless substances. The method has good treatment effect, but has strict requirements on the environmental water quality and high cost.
The flocculation sedimentation method is a common treatment means in the current stage of sewage treatment, and utilizes a flocculating agent to destabilize and concentrate particles which are difficult to separate, and separate the particles by other modes. Due to the good effect and mature technology, the method is researched more, and the balance between the effect and the cost is realized mainly by optimizing and adjusting the flocculating agent. Polyacrylamide is a commonly used flocculant with many advantages over other agents. The polymer can expand the performance thereof in a modification mode to adapt to sewage treatment with different indexes, and the modified flocculant is mainly classified into an anionic type, an amphoteric type, a cationic type and a hydrophobic association type.
The cationic polyacrylamide has high positive charge density, good water solubility and excellent turbidity removal, oil removal, flocculation and adsorption capacities, and is used as an important component of the high-efficiency sewage purifying agent. However, because of the large number of products of the existing cationic polyacrylamide, the change of the structure and the functional group of the cationic polyacrylamide can also influence the practical effect of the flocculant.
Disclosure of Invention
In order to solve the problems of the prior art, the present invention provides a flocculant and a preparation method for preparing the same, in which an optimal precipitation effect is obtained by defining a copolymer structure, a polymerization monomer, a cationic degree, and the like of the flocculant, and a preparation method capable of preparing such a specific copolymer.
The technical scheme adopted by the invention is as follows:
in a first aspect, the present invention discloses a flocculant as a formulated emulsion comprising a copolymer formed by polymerizing a plurality of monomers, the copolymer comprising:
a polyacrylamide monomer as a main monomer group, and
poly-N, N-dimethyl-octadecyl allyl ammonium chloride monomer as ionic monomer group, and
cetyl polyacrylate monomers as the hydrophobic monomer group;
wherein the ionic monomer is embedded on the polyacrylamide carbon chain to form a block type copolymer, the cationic degree in the copolymer is 20-50%, and the viscosity average molecular weight is 300-500 ten thousand.
It is worth noting that the hydrophobically associating cationic terpolymer formed by the addition of ionic monomers and hydrophobic monomers forms a flocculant with better performance than existing polyacrylamide polymers. The method is characterized in that conventional dimethyl diallyl ammonium chloride (DMDAAC) is not selected as a material of an ionic monomer group, conventional acrylate or vinyl acetate is not selected as a material of a hydrophobic monomer group, the requirements of high molecular weight and high stability are mainly considered to be met when the existing ionic monomer and hydrophobic monomer are polymerized, an alkene monomer with a substituent group as an electricity supply group is beneficial to cationic polymerization in principle, and alkyl is beneficial to controlling the structure control of a polymer along with the increase of a carbon chain.
Wherein, the block copolymer is a linear copolymer formed by alternately polymerizing different chain segments with different chemical structures. It can combine the excellent properties of various polymers to obtain functional polymer material with excellent performance. The polymer has controllable molecular weight, narrow molecular weight distribution and designable molecular structure and composition.
The cationic degree is a parameter definition of the copolymer, and the cationic degree can be used as one of the influence factors influencing the molecular weight of the whole copolymer. Meanwhile, the flocculation effect of the flocculating agent on different types of sewage is adjusted by adjusting the cationic degree, and the sedimentation and dehydration performance of flocculation products are also adjusted. The cationicity of the conventional cationic monomer in the prior art can not be used as a reference, different cationic monomer contents correspond to different product indexes, and particularly the parameter has influence on the preparation and use processes of the copolymer, so that the optimal copolymer product is obtained by targeted limitation, and the optimal copolymer product has the efficiency and the product stability in the preparation process, the flocculation effect of the flocculant containing the copolymer on different types of sewage and the like.
The added hydrophobic monomer enables the copolymer taking polyacrylamide as a main body to have the property of hydrophobic association, so that the spatial conformation of the polymer becomes more stretched through the association between hydrophobic molecular chains, and a three-dimensional network structure is formed.
In combination with the first aspect, the present invention provides the first embodiment of the first aspect, wherein the cationic degree in the copolymer is 35-45%, and the viscosity average molecular weight is 400-500 ten thousand.
In combination with the first aspect, the present invention provides a second embodiment of the first aspect, wherein the copolymer has a cationicity of 40% and a viscosity average molecular weight of 450 ten thousand.
In combination with the first aspect or the first or second embodiment of the first aspect, the present disclosure provides a third embodiment of the first aspect, wherein the mass fraction of the copolymer in the flocculant emulsion is 0.4 to 0.6%.
In a second aspect, the present invention discloses a method for preparing a flocculant according to the first aspect or the first or second embodiment of the first aspect, wherein a monomer raw material is polymerized in suspension in a dispersion system by an initiator to form a copolymer.
In combination with the second aspect, the present disclosure provides a first embodiment of the second aspect, wherein the initiator includes an azo initiator and an inorganic peroxide initiator;
wherein the mass ratio of the monomer, the ionic monomer and the initiator is (210-) -250): (50-90): (0.045-0.082).
In combination with the first embodiment of the second aspect, the present disclosure provides a second embodiment of the second aspect, wherein the initiator comprises the following components in a mass ratio of 3.7: 3.7: 2.6 azobisisopropylimidazoline hydrochloride, azobisisobutyramidine hydrochloride, and ammonium persulfate.
With reference to the second embodiment of the second aspect, the present invention provides a third embodiment of the second aspect, including the following specific steps:
s1, dissolving an acrylamide monomer, an N, N-dimethyl-octadecyl allyl ammonium chloride monomer, a polyacrylate monomer and EDTA in an anhydrous sodium sulfate aqueous solution, and uniformly stirring to obtain solution A;
s2, preparing initiators of azodiisopropyl imidazoline hydrochloride, azodiisobutyl amidine hydrochloride and ammonium persulfate according to a proportion to obtain a solution B;
s3, adding the solution A into a flask in a water bath environment, adjusting the water bath temperature to 60 ℃, introducing inert gas into the flask to exhaust air, and stirring at the rotating speed of 300-500r/min to disperse the monomers into liquid beads;
and S4, dropwise adding the prepared liquid B into the liquid A, raising the temperature of a water bath to 70 ℃ after the dropwise addition is finished, reacting, taking out the flask after the mixed solution becomes transparent and sticky, and cooling to finish the reaction.
In the invention, a plurality of monomers are suspended in a dispersion medium in a small drop shape in a mode of aqueous two-phase dropwise suspension polymerization in the preparation process, the monomer drops are converted into polymer solid particles, and a polymer-monomer viscous particle stage is performed in the middle. In order to prevent the particles from sticking to each other, a dispersant is added to the system so as to form a protective film on the surfaces of the particles. The reaction mechanism of suspension polymerization is the same as that of bulk polymerization, and is divided into homogeneous polymerization and precipitation polymerization. The particle size of the suspension polymer is about 0.05-2 mm, and is controlled mainly by stirring and dispersion.
Different from the condition limitation on the copolymer, the copolymer can be prepared by the method, and meanwhile, the method has lower cost, higher preparation efficiency and higher purity of the finished product.
In combination with the third embodiment of the second aspect, the present invention provides a fourth embodiment of the second aspect, wherein the mass ratio of the deionized water to the monomers added to the solution a is 100: 25.
In combination with the third embodiment of the second aspect, the present invention provides a fifth embodiment of the second aspect, wherein the mass ratio of the deionized water to the initiator in the prepared solution B is 100: 0.34.
The invention has the beneficial effects that:
(1) the copolymer in the flocculant is hydrophobic association type polyacrylamide formed by cationic monomers, the viscosity of the system is low, the polymerization heat is easy to be led out, and the generated flocculant has better flocculation effect;
(2) the invention controls the molecular weight of the copolymer by limiting the cationic degree in the special copolymer so as to achieve better flocculation effect under the control of lower cost and realize electrostatic adsorption of impurities in water through charged groups;
(3) the invention obtains the best polymerization effect by limiting the conditions of the manufacturing process, including the double water phase dripping mode, the temperature, the initiator category, the initiator-monomer ratio and the initiator concentration in the suspension polymerization, so that the polymerization rate is accelerated, the formed polymer is stable, and the polymerization reaction is easy to terminate;
(4) the invention limits the copolymer concentration of the flocculant emulsion, utilizes the characteristics of the copolymer to comprehensively treat sewage with different indexes, and ensures the flocculation effect as much as possible on the premise of reducing the use cost.
Drawings
FIG. 1 is a graph of the potential distribution with cationic degree in an aqueous solution of samples of copolymers of different cationic degrees according to examples of the present invention;
FIG. 2 is a graph showing the variation of molecular weight with cationicity of a sample of a copolymer synthesized in an example of the present invention
FIG. 3 is a graph of the amount of copolymer used as a function of suspended solids in wastewater for an example of the present invention;
FIG. 4 is a graph showing the variation of total phosphorus in wastewater with the amount of flocculant after the wastewater is treated with a 40% cationicity sample and polyaluminium chloride according to the example of the present invention;
FIG. 5 is a graph showing the comparison of the effect of the sample with cationic degree of 0.6% and 40% by mass on the sewage before and after the sewage treatment in the example of the present invention;
FIG. 6 is a graph comparing the effect of treatment of samples of different copolymer mass concentrations and polyaluminum chloride on kaolin suspensions in examples of the invention;
FIG. 7 is a graph showing the viscosity average molecular weight of a polymer emulsion according to the concentration by mass of the solution A in the example of the present invention;
FIG. 8 is a graph of viscosity average molecular weight of a polymer emulsion as a function of concentration in initiating system B in an example of the present invention;
FIG. 9 is a graph showing the temperature of the initiation system as a function of the viscosity average molecular weight of the polymer emulsion in accordance with an embodiment of the present invention;
FIG. 10 is a plot of emulsion polymerization time versus viscosity average molecular weight for examples of the present invention;
FIG. 11 is a reaction equation of a polymerization reaction in the example of the present invention.
Detailed Description
The present invention will be further explained with reference to specific examples.
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are some embodiments of the present application, but not all embodiments. The components of the embodiments of the present application, generally described and illustrated in the figures herein, can be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the present application, presented in the accompanying drawings, is not intended to limit the scope of the claimed application, but is merely representative of selected embodiments of the application. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
It should be noted that: like reference numbers and letters refer to like items in the following figures, and thus, once an item is defined in one figure, it need not be further defined and explained in subsequent figures.
Example 1:
this example discloses a flocculant, which is an emulsion prepared according to the type of wastewater, and mainly comprises a copolymer of several monomers formed by suspension polymerization.
The copolymer comprises a main monomer group, an ionic monomer group and a hydrophobic monomer group. The main monomer adopts conventional acrylamide, the ionic monomer adopts unconventional cationic monomer N, N-dimethyl-octadecyl allyl ammonium chloride, and the hydrophobic monomer adopts unconventional hexadecyl acrylate.
Wherein, polyacrylamide is a main chain, N-dimethyl-octadecyl allyl ammonium chloride is embedded on a carbon chain of the polyacrylamide, the cationic degree control range is between 20 and 50 percent, the molecular weight of the obtained copolymer takes the viscosity average molecular weight as a reference, and the index is 500 ten thousand.
This example also discloses the process for the preparation of the flocculant by first preparing the copolymer on-line. Dissolving an acrylamide monomer, an N, N-dimethyl-octadecyl allyl ammonium chloride monomer, a polyacrylate monomer and EDTA (ethylene diamine tetraacetic acid) serving as a dispersing agent in an anhydrous sodium sulfate aqueous solution, and uniformly stirring to obtain solution A; preparing initiator azodiisopropyl imidazoline hydrochloride, azodiisobutyl amidine hydrochloride and ammonium persulfate according to a proportion to obtain solution B; adding the solution A into a flask in a water bath environment, adjusting the temperature of the water bath to 60 ℃, introducing inert gas into the flask to exhaust air, and stirring at the rotating speed of 300-500r/min to disperse the monomers therein into liquid beads; and dropwise adding the prepared solution B into the solution A, raising the temperature of a water bath to 70 ℃ after the dropwise addition is finished, reacting, and obtaining a copolymer product reaching the standard after the mixed solution becomes a transparent viscous form.
And then taking out the flask for cooling, taking out the crude product of the copolymer emulsion, repeatedly washing and filtering, and baking and drying at low temperature for a certain time to obtain a solid finished product of the copolymer. The solid finished product is matched with deionized water, and the mass fraction of the copolymer is 0.4-0.6%, so that the flocculant emulsion is obtained.
In order to increase the molecular weight of the polymer and improve the stability and the polymerization efficiency of the copolymer, the preparation process conditions and the raw material ratio are preferably selected.
In some embodiments, the mass ratio of monomer, cationic monomer, and initiator is 210: 90: 0.045, and wherein the initiator comprises a mass ratio of 3.7: 3.7: 2.6 of azobisisopropylimidazoline hydrochloride, azobisisobutyramidine hydrochloride, and ammonium persulfate.
Preferably, the mass ratio of the added deionized water to the monomer in the prepared solution A is 100: 25;
in the prepared solution B, the mass ratio of the added deionized water to the initiator is 100: 0.34.
at this time, according to the above-mentioned defined conditions, a copolymer sample was prepared in a laboratory and tested, 15g of AM, 15g of N, N-dimethyl-octadecyl allyl ammonium chloride, 1.8g of urea, and 0.5g of hexadecyl acrylate were sequentially added to a 250mL three-necked flask, and dissolved in 67.7g of an anhydrous sodium sulfate solution to prepare solution A, and the mixture was stirred at a rate of 200r/min for 30min under nitrogen gas blanket.
0.0012g of azobisisobutyramidine hydrochloride (V044), 0.0012g of azobisisobutyramidine hydrochloride (V50), and 0.0008g of ammonium persulfate were dissolved in 5mL of deionized water to prepare solution B. And (3) dropwise adding the prepared solution B into the solution A by using a peristaltic pump for about 30min, heating the water bath to 70 ℃ after dropwise adding, and reacting for 5 h. When the solution is changed into transparent viscous liquid, the cation degree of the detector is 50%.
In some embodiments, the mass ratio of monomer, cationic monomer, and initiator is 220: 80: 0.055, and wherein the initiator comprises a molar ratio of 3.7: 3.7: 2.6 of azobisisopropylimidazoline hydrochloride, azobisisobutyramidine hydrochloride, and ammonium persulfate.
Preferably, the mass ratio of the added deionized water to the monomer in the prepared solution A is 100: 25;
in the prepared solution B, the mass ratio of the added deionized water to the initiator is 100: 0.34.
at this time, according to the above-mentioned defined conditions, a copolymer sample was prepared in a laboratory and tested, 18g of AM, 12g of N, N-dimethyl-octadecyl allyl ammonium chloride, 1.8g of urea, and 0.5g of hexadecyl acrylate were sequentially added to a 250mL three-necked flask, and dissolved in 67.7g of an anhydrous sodium sulfate solution to prepare solution A, and the mixture was stirred at a rate of 200r/min for 30min under nitrogen gas blanket.
0.0012g of azobisisobutyramidine hydrochloride (V044), 0.0012g of azobisisobutyramidine hydrochloride (V50), and 0.0008g of ammonium persulfate were dissolved in 5mL of deionized water to prepare solution B. And dropwise adding the prepared solution B into the solution A by using a peristaltic pump for about 30min, heating the water bath temperature to 70 ℃ after dropwise adding is finished, and reacting for 5 h. When the solution becomes transparent viscous liquid, the cation degree of the detector is 40%.
In some embodiments, the mass ratio of monomer, cationic monomer, and initiator is 230: 70: 0.065, and wherein the initiator comprises a mass ratio of 3.7: 3.7: 2.6 of azobisisopropylimidazoline hydrochloride, azobisisobutyramidine hydrochloride, and ammonium persulfate.
Preferably, the mass ratio of the added deionized water to the monomer in the prepared solution A is 100: 25;
in the prepared solution B, the mass ratio of the added deionized water to the initiator is 100: 0.34.
at this time, according to the above-mentioned defined conditions, a copolymer sample was prepared in a laboratory and tested, 21g of AM, 9g of N, N-dimethyl-octadecyl allyl ammonium chloride, 1.8g of urea, and 0.5g of hexadecyl acrylate were sequentially added to a 250mL three-necked flask, and dissolved in 67.7g of an anhydrous sodium sulfate solution to prepare solution A, and the mixture was stirred at a rate of 200r/min for 30min under nitrogen gas blanket.
0.0012g of azobisisobutyramidine hydrochloride (V044), 0.0012g of azobisisobutyramidine hydrochloride (V50), and 0.0008g of ammonium persulfate were dissolved in 5mL of deionized water to prepare solution B. And (3) dropwise adding the prepared solution B into the solution A by using a peristaltic pump for about 30min, heating the water bath to 70 ℃ after dropwise adding, and reacting for 5 h. When the solution is changed into transparent viscous liquid, the cation degree of the detector is 30%.
In some embodiments, the mass ratio of monomer, cationic monomer, and initiator is 250: 50: 0.065, and wherein the initiator comprises a mass ratio of 3.7: 3.7: 2.6 azobisisopropylimidazoline hydrochloride, azobisisobutyramidine hydrochloride, and ammonium persulfate.
Preferably, the mass ratio of the added deionized water to the monomers in the prepared solution A is 100: 25.
The curve of the viscosity-average molecular weight of the polymer emulsion changing with the mass concentration of the solution A is shown in FIG. 7, in the whole polymerization reaction process, the viscosity-average molecular weight of the polymer is firstly increased and then decreased with the mass concentration of the monomer A, and according to the principle of free radical polymerization, when the mass fraction of the monomer is lower, the polymerization rate is lower, the free radicals generated by the monomer are less, and the viscosity-average molecular weight is lower. The mass fraction of the monomer is too high, the polymerization rate is too fast due to more generated free radicals, the polymerization heat in a polymerization system is not easy to dissipate, the rapid temperature rise easily causes 'implosion', the molecular weight is too low, and therefore the optimal mass ratio of the monomer solution A is finally determined to be 100: 25.
And in the prepared solution B, the mass ratio of the added deionized water to the initiator is 100: 0.34.
The curve of the viscosity-average molecular weight of the polymer emulsion changing with the concentration of the initiating system B is shown in FIG. 8, the influence of the concentration of the initiating agent on the polymerization effect in the free radical polymerization reaction is relatively large, and the viscosity-average molecular weight of the polymer increases firstly and then decreases with the increase of the concentration of the initiating agent. When the concentration of the initiator is lower, the content of free radicals generated by the monomer for induced polymerization is relatively lower, the half-life period is short, and the induced factors cannot diffuse in time to form stable molecules and cannot initiate the monomer to generate free radicals for polymerization. When the concentration of the initiator is higher, the number of free radicals generated by induction is larger, and the polymerization heat is not easy to dissipate and is easy to 'implode' to influence the viscosity-average molecular weight of the product. Thus, the optimum mass concentration of A was finally determined to be 100: 0.34.
In this case, the copolymer prepared under the above conditions had a cationicity of 20%.
Then, according to the above-defined conditions, a copolymer sample was prepared in the laboratory and tested, 24g of AM, 6g of N, N-dimethyl-octadecyl allyl ammonium chloride, 1.8g of urea, and 0.5g of hexadecyl acrylate were sequentially added to a 250mL three-necked flask, dissolved in 67.7g of anhydrous sodium sulfate solution to prepare solution A, and the mixture was stirred at 200r/min for 30min under nitrogen blanket.
0.0012g of azobisisobutyramidine hydrochloride (V044), 0.0012g of azobisisobutyramidine hydrochloride (V50), and 0.0008g of ammonium persulfate were dissolved in 5mL of deionized water to prepare solution B. And (3) dropwise adding the prepared solution B into the solution A by using a peristaltic pump for about 30min, heating the water bath to 70 ℃ after dropwise adding, and reacting for 5 h. When the solution is changed into transparent viscous liquid, the cation degree of the detector is 30%.
The above embodiments are only referred to some embodiments provided for the parameter range defined by the present invention, the present invention is not limited to the above alternative embodiments, and any other various forms of products can be obtained by anyone in the light of the present invention. The above detailed description should not be taken as limiting the scope of the invention, which is defined in the claims, and which the description is intended to be interpreted accordingly.
In this embodiment, in order to detect the influence of the corresponding condition limitations on the molecular weight and stability of the finished flocculant and the influence of the flocculation effect of the flocculant after the flocculant emulsion is prepared, experimental tests are respectively performed.
The related limiting conditions comprise monomer raw material types, monomer raw material ratios, formed polymer structures, initiator types, initiator ratios, solvent systems, polymerization modes, polymerization temperatures, A droplet adding concentrations and B droplet adding concentrations.
The parameters to be measured comprise cationic degree, Zeta potential, viscosity-average molecular weight, suspended matter content of the flocculant prepared emulsion and added in the sewage sample, total phosphorus and light transmittance of supernatant after precipitation.
The main reagents involved are as follows:
analytically pure acrylamide
70% N, N-dimethyl-octadecyl allyl ammonium chloride solution
Analytically pure cation substitutes
Analytically pure urea
Analytically pure cetyl acrylate
Analytically pure hydrophobic monomer substitute
Analytically pure azodiisopropylimidazoline hydrochloride (V044)
Analytically pure azodiisobutyamidine hydrochloride (V50)
Analytically pure ammonium persulfate
Analytically pure initiator substitutes (other azo initiators, organic and inorganic peroxides, etc.)
Analytically pure EDTA
Emulsifier
The test equipment involved is as follows:
flat bottom flask
Electronic balance
Electric heating constant temperature water bath
Spectrophotometer
Zeta potential analyzer
Peristaltic pump
Vacuum pump
Electric mixer
Electrothermal blowing dry box
Infrared spectrometer
Ubbelohde viscometer
Plunger measuring cylinder
Syringe with a needle
The analytical calculation method involved is as follows:
a. the expression of the homogeneous molecular weight test is:
in the formula:
is viscosity average molecular weight, Ni、MiThe number of molecules and the molecular weight of the component i; alpha is a parameter of the MHS equation and is related to the nature of the solvent of the solution at a certain temperature. The formula is derived based on the additivity of the increasing viscosity with the concentration approaching zero, and then is further derived by using an MHS equation. The test method is to calculate the flow-out time of the solution and the flow-out time of the pure solvent by using an Ubbelohde viscometer.
b. Determination of degree of cationicity
The cationicity was determined by colloid titration. The dried cationic polyacrylamide (to the nearest 0.0001g) was weighed out on a weighing paper into a 250mL weighing bottle and 100mL of distilled water was added. After stirring until dissolved, the pH was adjusted, the t.b. indicator was added and titrated with the prepared standard solution. The titration end point is determined when the solution changes from blue to red-purple. At least three parallel groups are made, and the average consumed volume is recorded as V1(ii) a At the same time, a blank experiment was performed, and the volume of the consumed solution was recorded as V.
And the cationic degree calculation formula is as follows:
in the formula: a. themIs the cation degree of the solution; c is the solution molar concentration, mol/L; v is the volume of solution consumed during titration, V0The volume of solution consumed in the blank, mL; m is the mass of the sample, g; 207.5 is the relative molecular mass of the cationic segment, exemplified here by methacryloxyethylammonium chloride.
Zeta potential measurements were first performed on samples with different gradients of cationicity prepared in the above examples to reflect the stability of the polymer with different cationicity.
The sample was measured by a Zeta potential analyzer, and the specific structure is shown in FIG. 1, in which it can be seen that the Zeta potential value of the copolymer is increased with the increase of the cationic degree. According to the judgment of experience, when the Zeta potential value is higher than 30mV, the stability of the whole polymer can meet the basic requirement.
Then, molecular weight measurements were also performed on samples with cationicity of 20%, 30%, 40% and 50%, and the results are shown in fig. 2. It can be seen that when the cationicity is less than 40%, the whole curve tends to increase monotonically, especially in the range from 30% to 40%, the molecular weight increase is large and peaks around 40%, and at 50%, the molecular weight is significantly reduced. From the aspect of molecular weight, when the cationic degree is about 40%, the prepared cationic hydrophobic association type polyacrylamide flocculant has higher relative molecular weight and higher polymerization degree, so that 40-Y-PAM (polyacrylamide flocculant with the cationic degree of 40%) is selected as a preferable product.
Furthermore, in order to verify the treatment effect of the copolymer emulsions with different concentrations on substances in different sewage, different sewage treatment samples are prepared for corresponding treatment.
1000mL of pretreated sewage is weighed, mechanically stirred at the rotating speed of 300r/min, added with 0.1% of diluted prepared Y-PAM type polymer, and stirred for 20S. And pumping and filtering the prepared sample to ensure that the water completely passes through the filter membrane, and taking out the filter membrane loaded with the suspended matters. Specifically, the detection and analysis of suspended solid (TSS) in the solution are carried out according to the wastewater suspended matter standard GB/11901-89, and the result is shown in FIG. 3. As can be seen in FIG. 3, the suspended matter concentration content is kept in a significantly decreasing trend within the range of 0.1% to 0.4% by mass concentration. And when the mass concentration is higher than 0.4%, the reduction area of the suspended matter content is gentle, and when the mass concentration reaches 0.6%, the suspended matter concentration approaches 0, which indicates that the mass concentration range of 0.4% -0.6% belongs to the optimal cost control interval. Although the quality concentration is continuously increased, a better flocculation effect can be obtained, the promotion amplitude is smaller, and the input-output ratio is lower.
Then, 1000mL of pretreated sewage was measured, mechanically stirred at a rotation speed of 300r/min, added with 0.1% diluted Y-PAM type polymer, and stirred for 20S. The prepared sample is sucked and filtered, and the supernatant is taken to perform detection analysis on the total phosphorus in the treated water according to the national sewage treatment analysis GB/11893-89, and the result is shown in figure 4, wherein the content of P in the sewage is reduced along with the increase of the concentration of the polymer. When the concentration of the polymer is increased to 0.6 percent, the phosphorus content in the treated sewage can meet the national sewage quality analysis GB 8978-1996-Integrated wastewater discharge Standard. As described above, the economic efficiency is highest in the range of approximately 0.6%.
Then, the flocculation effect evaluation is carried out, and a polymer sample and polyaluminium chloride are prepared into a flocculant solution with the mass fraction of 1.0 per mill in a constant-temperature water bath kettle at the temperature of 30 ℃. Two parts of 2.0% kaolin suspension are placed in a 100mL plunger measuring cylinder, two flocculant solutions with set amounts are respectively added by a syringe, the plunger measuring cylinder is tightly plugged and is inverted up and down for 10 times, after standing for 5min, 70mL of supernatant is taken by a 25mL pipette, and the light transmittance is measured by a 722 grating spectrophotometer (the flocculation effect is represented by the light transmittance). The results are shown in FIG. 6, and the flocculation effect of 40-Y-PAM is obviously better than that of polyaluminium chloride under the same conditions. The molecular chain of the charged group is more stretched in the aqueous solution, which is beneficial to both electric neutralization and flocculation.
The above experimental mode is to perform effect verification or description of a preferable process on preferable results of the whole flocculant configuration fraction and the cation concentration, and the selection of the special monomer and the initiator adopted in the invention is also important for the product effect, so the experimental verification is performed in order to verify the selection specificity of the monomer and the initiator. The following table shows the polymerization and residual monomer parameters for different initiation systems using the methods disclosed in the above examples.
TABLE 1
It should be noted that the system belongs to a free radical polymerization reaction, and the growth rate of a molecular chain is closely related to the concentration of free radicals in the system. In order to obtain a polymer of high molecular weight, it is important to maintain a suitable concentration of free radicals in the polymerization system. Since the initiation system is an intermediate product of the polymerization of monomers by electron transfer, the polymerization rate is critical in determining the relative molecular weight of the product, which is free radical initiated polymerization. In the later stage of polymerization reaction, the concentration of the produced free radicals is greatly reduced, the chain termination reaction speed is increased quickly, and the delayed chain termination is a measure for effectively improving the relative molecular weight, so that a composite initiation system is adopted, the polymerization reaction is completed in a layered and segmented gradual initiation mode, the proper initiation system is determined by combining different activation energies of different types of initiators and different temperature conditions for releasing the produced free radicals, the polymerization reaction speed is controlled, the viscosity average molecular weight of a polymerization product can be effectively improved, and the polymerization is promoted. Therefore, a hierarchical initiation system consisting of ammonium persulfate, azodiisopropyl imidazoline hydrochloride and azodiisobutyl amidine hydrochloride is finally selected.
The effect of the unused cationic monomer on the adsorption effect of the subsequent flocculant is then different. The flocculation effect for different cationic monomer polymer systems in the same increase is shown in table 2.
TABLE 2
The results show that for the polymer system of the cationic monomer, the smaller the carbon chain skeleton of the cationic monomer is not beneficial to flocculation, and the longer the carbon chain is, the more beneficial the flocculation is, so that N, N-dimethyl-octadecyl allyl ammonium chloride is selected as the cationic monomer in the research.
While different hydrophobic monomers mainly affect the flocculation effect during the flocculation process, this example was evaluated by the critical aggregation concentration CAC, and the results of the test by replacing the flocculation with several hydrophobic monomers commonly available on the market are shown in table 3.
TABLE 3
It can be seen from the table that for the conventional short chain selected hydrophobic monomers, there is no critical aggregation concentration CAC. The hydrophobic properties are slightly less hydrophobic than cetyl acrylate, so this study selects cetyl acrylate as the hydrophobic monomer.
Different salt solutions also had an effect on the polymerization performance of the polymerization system, and the results of the test by replacing different salt solutions are shown in Table 4.
TABLE 4
The table shows that different systems of monovalent salt and divalent salt are researched and compared, the divalent salt has higher charge cloud density and stronger electrostatic repulsion, has stronger compression effect on free radicals generated by polymerization, is easy to cause unstable polymerization of the system through sudden polymerization, and the sodium chloride system has good solubility but has difficultly controlled reaction rate. Therefore, an anhydrous sodium sulfate system is ultimately preferred as the dispersion system for the emulsion polymerization of this study.
Since the initiation temperature is also defined in this example, and this temperature is related to the change in molecular weight of the polymer emulsion, it needs to be verified. The temperature of the initiation system is shown in FIG. 9 as a function of the viscosity average molecular weight of the polymer emulsion. The graph shows that as the initiation temperature increases, the viscosity average molecular weight of the polymer emulsion increases and then decreases, ultimately determining an initiation temperature of 60 ℃. The reaction belongs to free radical polymerization, the initiation temperature of a system determines the rate of free radicals released by an initiator, the temperature is too low, and the rate of free radicals released by the initiator of the system is preferably low, so that the polymerization degree of a polymerization monomer is influenced; the system temperature is higher, the free radical releasing rate of the initiating system is too fast, and the system is easy to implode, so that the proper initiating system temperature has great influence on the viscosity average molecular weight of the polymer emulsion.
The curve of the emulsion polymerization time and the viscosity-average molecular weight is shown in fig. 10, for the polymerization reaction, incomplete polymerization is caused by too short reaction time, more residual monomers in the system affect the viscosity-average molecular weight of the product, and the reaction time is too long and consumes time and energy, and as can be seen from the results in fig. 10, the viscosity-average molecular force of the polymer emulsion tends to be stable after 3 hours of reaction, so 3 hours is selected as the optimal time for the polymerization reaction of the system.
Claims (10)
1. A flocculant as a solid material for formulating an emulsion comprising a copolymer formed by polymerizing a plurality of monomers, the copolymer comprising:
a polyacrylamide monomer as a main monomer group, and
poly-N, N-dimethyl-octadecyl allyl ammonium chloride monomer as ionic monomer group, and
a hexadecyl polyacrylate monomer as a hydrophobic monomer group;
wherein the ionic monomer is embedded on the polyacrylamide carbon chain to form a block type copolymer, the cationic degree in the copolymer is 20-50%, and the viscosity average molecular weight is 300-500 ten thousand.
2. The flocculant as claimed in claim 1, wherein the cationicity of the copolymer is 35-45%, and the viscosity average molecular weight is 400-500 ten thousand.
3. The flocculant of claim 1, wherein the cationicity of the copolymer is 40% and the viscosity-average molecular weight is 450 ten thousand.
4. A flocculating agent according to any of claims 1 to 3 wherein the copolymer is present in the formulated emulsion in a mass fraction of from 0.4 to 0.6%.
5. A method for producing a flocculating agent, characterized in that, for producing a flocculating agent according to any of claims 1 to 3, the monomer raw materials are polymerized in suspension in a dispersion by means of an initiator to form a copolymer.
6. The method according to claim 5, wherein the initiator comprises azo initiator and inorganic peroxide initiator;
wherein the mass ratio of the monomer, the cationic monomer and the initiator is (210-): (50-90): (0.045-0.082).
7. The method for preparing the flocculant according to claim 6, wherein the initiator comprises the following components in a mass ratio of 3.7: 3.7: 2.6 azobisisopropylimidazoline hydrochloride, azobisisobutyramidine hydrochloride, and ammonium persulfate.
8. The preparation method of the flocculant according to claim 7, characterized by comprising the following specific steps:
s1, dissolving an acrylamide monomer, an N, N-dimethyl-octadecyl allyl ammonium chloride monomer, a polyacrylate monomer and EDTA (ethylene diamine tetraacetic acid) serving as a dispersant into an anhydrous sodium sulfate aqueous solution, and uniformly stirring to obtain a solution A;
s2, preparing initiators of azodiisopropyl imidazoline hydrochloride, azodiisobutyl amidine hydrochloride and ammonium persulfate according to a proportion to obtain a solution B;
s3, adding the solution A into a flask in a water bath environment, adjusting the water bath temperature to 60 ℃, introducing inert gas into the flask to exhaust air, and stirring at the rotating speed of 300-500r/min to disperse the monomers into liquid beads;
and S4, dropwise adding the prepared liquid B into the liquid A, raising the temperature of a water bath to 70 ℃ after the dropwise addition is finished, reacting, taking out the flask after the mixed solution becomes transparent and sticky, and cooling to finish the reaction.
9. The method for preparing the flocculating agent according to claim 8, wherein the mass ratio of the deionized water to the monomers added in the prepared solution A is 100: 25.
10. The method of claim 8, wherein the mass ratio of the deionized water to the initiator in the prepared solution B is 100: 0.34.
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